Fixed volatile flavors and method for making same

ABSTRACT

VOLATILE FLAVORING COMPOUNDS SUCH AS ACETALDEHYDE ARE FIXED IN LOW AMOUNTS BY HAVING THE COMPOUND PRESENT IN SOLUTION DURING THE CRYSTALLIZATION OF SUCH EDIBLE MATERIALS AS SUCROSE, MANNITOL, AND SODIUM CHLORIDE. IT IS BELIEVED THAT HTE VOLATILE FLAVOURS ARE ENTRAPPED AS IMPURITIES WITHIN THE CRYSTAL STRUCTURE. THE RESULTING COMPOSITIONS HAVE EXCELLENT STABILITY OVER A WIDER RANGE OF HUMIDITIES, ARE SOLUBLE IN BOTH HOT AND COLD WATER, AND HAVE APPLICATION AS FLAVOR AND AROMA MODIFIERS FOR FOODS.

United States Patent ()flice 3,787,592 Patented Jan. 22, 1974 3,787,592 FIXED VOLATILE FLAVORS AND METHOD FOR MAKING SAME William Alexander Mitchell, Lincoln Park, NJ., and Howard Dave Stahl, Tarrytown, and William Charles Seidel, Monsey, N.Y., assignors to General Foods Corporation, White Plains, N.Y.

No Drawing. Filed May 12, 1970, Ser. No. 36,666 Int. Cl. A23l 1/26 US. Cl. 426-380 11 Claims ABSTRACT OF THE DISCLOSURE Volatile flavoring compounds such as acetaldehyde are fixed in low amounts by having the compound present in solution during the crystallization of such edible materials as sucrose, mannitol, and sodium chloride. It is believed that the volatile flavors are entrapped as impurities within the crystal structure. The resulting compositions have excellent stability over a wide range of humidities, are soluble in both hot and cold water, and have application as flavor and aroma modifiers for foods.

BACKGROUND OF THE INVENTION This invention relates to volatile food flavoring compounds such as flavors, flavor enhancers, aromas, and aroma enhancers, and more particularly to volatile flavoring compounds such as acetaldehyde, fixed in crystalline food materials such as sucrose to form solid flavoring compositions which are stable under normal shelf storage conditions, but which release flavoring when combined with either hot or cold water.

It has been known for some time that flavoring compounds such as acetaldehyde are important flavor components of natural fruits and vegetables and serve as flavor enhancers for the various flavor notes naturally present in meats, fruits and vegetables. Particularly, it has been found that acetaldehyde is very important in increasing the impact and freshness of certain flavors, such as fruittype flavors. However, while the presence of acetaldehyde would be a valuable enhancer to a synthetic flavoring composition for use with a food formulation employing fruity-type flavors, it is diflicult to incorporate acetaldehyde into a stable, solid flavor fixative. Most attempts to fix acetaldehyde in various compositions have tended to be unstable in the presence of small amounts of water or water vapor. This stability problem was apparent when powdered dessert and beverage products containing the fixed acetaldehyde was processed or packaged in a manner allowing atmospheric or product moisture to reach the fixed acetaldehyde during storage 'of the product. This problem is particularly acute when a fruit-type dessert or beverage formulation using a fixed acetaldehyde flavor is packaged in dry form in a non-hermetically sealed paper envelope or container which is sufliciently pervious to allow atmospheric moisture to enter and react with or dissolve the acetaldehyde.

Acetaldehyde is chemically very reactive; it is very soluble in water; and it has a low boiling point (21 C.). It exists as a gas at normal room temperature and pressure. It, furthermore, is readily oxidized to form acetic acid, and it easily polymerizes to form paraldehyde and metaldehyde. Thus, the problem confronting the food industry in augmenting the flavor and aroma of dry powdered mixes has been that of fixing acetaldehyde in a sufliciently stable state to avoid volatilization and/or chemical reaction during storage. It also is necessary to limit the degree of fixation to permit the release of the acetaldehyde compound during the normal household preparation of rehydrating or otherwise preparing a finished table product from the powdered mix (e.g. by addition of either hot or cold water).

Generally speaking, there are two methods of fixing acetaldehyde to insure improvement in shelf stability. One method is to chemically react the acetaldehyde with another material to form a more stable compound. The second method is to physically entrap or coat the acetaldehyde with a stable compound such as sugar, gum or other edible material.

With respect to the first method-that of forming a more stable compound-the resulting composition must not only have a degree of stability and dissociability compatible with storage and subsequent use conditions, but it must also be a functional derivative type compound; that is, it must have an inherent chemical structure which will release acetaldehyde upon decomposition. Also the residual decomposition compound other than the acetaldehyde resulting from the breakdown of the functional derivative compound must not be detrimental to the quality of the finished food product. It is also essential that the breakdown take place under the conditions at which the food product is prepared or used.

Although many attempts, such as US. Pat. No. 2,305,- 621, have been made to produce suitable functional derivative compounds by reacting acetaldehyde with other chemical compounds, with few exceptions, they have not resulted in operational successes. The major causes of the failures have been instability of the resulting product or, conversely, too great a stability to provide utility.

The second method of physically encapsulating the acetaldehyde within a stable compound has not usually met with commercial success since the products prepared by this method have been in a glassy or amorphous state and have tended to lose their fixed flavor during storage especially in the presence of moisture.

A recently issued US. patent to Dame et al., No. 3,314,803 discloses a method of fixing acetaldehyde by encapsulating the acetaldehyde in a matrix of dry mannitol. This procedure has produced a dry, non-hydroscopic material which will retain a portion of its fixed acetaldehyde even under non-hermetic conditions, but has the disadvantage of being very costly because of the current price of mannitol. The spray-dried, mannitol-acetaldehyde composition of Dame et al., can have an initial fixation of 2% to 10% by weight of acetaldehyde. However, this initial fix will be modulated in several days and the level of acetaldehyde will equilibrate to a stable range usually between 1% t0 3%.

Generally, the prior art has indicated that in order to preserve flavor materials out of contact with the atmosphere, fixation should be achieved by means of amorphous matrix material. US. Pat. No. 2,856,291 to Schultz discloses that crystallization should be avoided since the crystal structure will enable the escape of the flavor materials or the permeation of the atmosphere into the flavoring composition through the interstices of the crystal structure. The Dame et al., patent discloses encapsulating the acetaldehyde within the mannitol matrix without crystallizing the mannitol.

volatile" flavor compounds as "acetaldehyd'e has been achieved by means of crystallizing an edible material such as sucrose from a solution containing the flavor compound. It has been discovered that small amounts of volatile flavoring materials can be fixed in crystalline materials in such a manner that the volatile material will be permanently fixed when stored under hermetic conditions and will retain much of the ,volatile material even after prolonged storage under non-hermetic conditions.

It is the general object of this invention to produce a moisture-stable flavoring material. containing volatile flavoring compounds. 7

It is a further object-of this invention to provide a nonhygroscopic, solid flavoring composition containing low (less than 1% by weight) amounts of a volatile flavoring compound which composition is cap-able of being mixed with powdered, fruit flavor mixes and which upon the addition of either hot or cold water during home preparation will enhance the flavor or aroma of a food product.

It is a specific object of this invention to produce a dry, non-hygroscopic, acetaldehyde containing composition which will retain acetaldehyde under conditions of both elevated temperature and humidity.

-It is a more specific object of this inventionto entrap low (less than 1%) levels of acetaldehyde within the crystals of edible carbohydrate materials such as sucrose and mannitol.

It is a most specific object of this invention to produce a powdered food composition containing a high portion of sucrose and which sucrose has entrapped within its crystal structure a low (less than 1%) levelof a volatile flavor compound such as acetaldehyde.

DESCRIPTION OF THE INVENTION Since the amount of volatile flavor that can beffixed by the method of this invention is relatively low, it iscontemplated that the commercial use of this invention; would employ a fixing material which is an integral part of:a food product. Sucrose is an example of a material which can be employed in this invention and which :is a normal component of many fruit flavored powdered food prod.-

ucts' such as gelatin dessert and beverage mixes. The use of such a material as sucrose to also act as a fixing 'rnedi um for a food flavoring compound such as acetaldehyde will permit the production of an improved food product with very little increase in the cost of raw materials; Sodium chloride is another crystalline material. which is often i used in large quantities in many foods (e.g. meats) and which can be used to fix volatile flavors .(e.g. smoked flavors) according to this invention. 1

It is also contemplated by this invention that the entrapment of the volatile flavoring compound Within su, crose crystals may be accomplished during the crystalliza-" tion step of the sugar refining operation. This would avoid the necessity of performing a subsequentcrystallization operation during the manufacture of the food product. 3

Another advantage of our invention is that crystalline fixations of acetaldehyde have been found to possess a cleanacetaldehyde taste, quite free of the paraldehyde taste. This occurs despite the fact that the acetaldehydesource contains significant amounts of paraldehyde. .It seems that this method of fixation fixes only the acetaldehyde while rejecting paraldehyde. r

f. invention is especially suited to. fix tli'oseflavor compounds which are gaseous or which sublime at normal roomconditions: As previously indicated it is believed that the volatile compound is thought to be fixed by means of crystal inclusion. An inclusion may be thought of as foreign matter which is imbedded in the crystal structure and not merely located on the surface of the crystal. The material fixed within the crystals cannot be washed out and tends to remain permanently fixed until the crystal structure is destroyed. It has been found that the volatile-flavors fixed in accordance with this invention are in fact unable to be washed out of the crystals and also that the crystalline fixationsare able to beheated up to temperatures of at least 100 C. without appreciable loss of the volatile compound.

The mechanism by which the volatile flavor compounds are ,occludedwithin thecrystal structure ot'fixing material during crystallization is thought to be approximated by amolecular model having a moleculeof theflavor compound surrounded -by'a'crystalcage consisting of a plurality of molecules of the fixing material. This mechanism is seen to difier from the inclusion complexes, exemplified by U.S.-Pa't. No. 3,061,444 to Rogers et al., where a molecule ofthe included compound is spatially fitted into a. molecule of a cylindrical or spiral shaped dextrin material. p Sugar and sugar derivatives such as sucrose and mannitol are two examples of crystal formingcarbohydrate.

materials that are successful in this invention. Other ma terials which form the appropriate crystal structure may also be employed in this invention. (For instance, success} ful results can ,be obtained from crystallizing an aqueous solution of an "inorganic salt such as sodium chloride or an organic acid such as-fumaric acid with acetaldehyde.

Not all crystal producing materials have been found to produce successful products. Carbohydrates .suchas dextrose and lactose which form crystal hydrates have been. found. to fix only very small traces of volatile. flavoring compounds, Isuch' as acetaldehyde, and are not considered to be acceptable. The reason why these crystal hydrates are unable to fix significant amounts of'yolatile flavoring compounds is not completely understood; howeverj it' is observed that the volatilecompounds do not eflfe ct the' rate of crystallization of such materials... This. is in con trast to the formation ,of anhydrous crystals of. such ma terials as 'sucr'ose andgmannitol whe'reithe. volatilecorn} pounds are seen to inhibitcrystallization and where it is thought that the crystals growaround the foreign material: to'frorm crystal inclusions. i

The'jcrystallization method used. to prodrl u'ct's ot'this invention comprises the formation of a super saturated solution, preferably aqueous'solutiom'of the crystallizable material, usually atatemperature-which is below the boiling pointof the volatile. compound. The

J volatile compound is then added tothe supersaturated so:

lution; and crystallization is allowed 'to pro ceed. Usually a small amount of 'seedma terial is added to the supersaturated solution in order to initiate crystalliza tionJThe'crystalsthus obtained; are sfeparat'ediandldried. The crystallization step may also'proce'e under'vac 11m c d ions Wh s rbt s y tih sl dehygle is equal to. or better than the fix levels under of the water will be removed under thevacuum'conditionsl" This invention is further illustrated by, but not limitedto, the following examples:

-EXAMPLE I.

A sucrose-water mixture'of 539 grams of sucrose and 161 grams of water were heated until all of the sucrose I that: a iQ ls of such fvolatile compounds as'acctalg dissolved. The solution was then cooled to below the boiling point of acetaldehyde (21 C.), or as in the case to C., producing a supersaturated solution of sucrose. Twenty-one mililiters of acetaldehyde (16.5 grams) were added slowly with stirring. One gram of powdered sucrose was added to initiate crystallization. The mixture was allowed to crystallize for two days although less time may have been adequate.

After crystallization was complete, the mixture appeared white and seemed to have dropped in viscosity. Crystals could be felt in the syrup. The mixture was added to the basket of an International Chemical Centrifuge Model 367-H which was spinning at high speed. The crystals were retained by the basket while the syrup passed through. The filter cake was removed from the basket and powdered by passing through a No. 30 US. mesh screen. The crystals were allowed to dry over night. This procedure yielded 200 grams of crystalline sucrose or 37.1% of the starting material. These crystals were analyzed by a polarographic procedure and found to contain 0.135% acetaldehyde. Organoleptically, the sucrose was found to have a clean acetaldehyde taste even thOugh the original acetaldehyde contained significant amounts of paraldehyde and did not have a clean taste.

The syrup obtained by centrifugation was saturated with sucrose and contained significant amounts of acetaldehyde. Additional sucrose may be added to the syrup and the mixture heated to obtain a solution of approximately 72% sucrose. Upon cooling the solution to below 21 C. additional acetaldehyde is added to produce a solution of approximately 2.3% acetaldehyde. The crystallization and centrifugation procedure are similar to those given above. In this manner, the total process may be considered cyclic and almost 100% efficient.

EXAMPLE II Ten grams of mannitol were dissolved in 55 ml. water at room temperature. To this solution were added 1.9 ml. acetaldehyde. Thirty grams of mannitol were dissolved in 30 ml. water by heating. This solution was added to the solution containing acetaldehyde. The total solution now consisted of 40 grams of mannitol, 85 ml. water, and 1.9 ml. acetaldehyde. Upon cooling the solution began to get viscous and milky in appearance. After about an hour and a half, crystalization was completed. The mannitol crystals were filtered and air dried. Organoleptically, the mannitol was found to have a clean aceltaldehyde taste. The material was analyzed and found to contain about 0.16% acetaldehyde.

EXAMPLE III Ten grams of mannitol were dissolved in 55 ml. of water at room temperature. To this solution was added 19 ml. of acetaldehyde. Fifty grams of mannitol were then dissolved in 50 ml. of water by heating. The two solutions were then combined and placed in a vacuum desiccator where a vacuum of 150 mm. of Hg was quickly achieved. After most of the water had been removed (about 60 minutes), the mannitol crystals were removed from the desiccator and air dried. The fix level of acetaldehyde was found to be 0.48%.

The material of Example I containing 0.135 acetaldehyde was evaluated for stability by packaging 7 grams of the sucrose fixed acetaldehyde (containing about 9.45 mg. of acetaldehyde) together with 85 grams of a standard-type gelatin dessert having a composition of:

TABLE Percent loss of RH. at F., Days acetaldepercent Storage hyde The stability data is quantitatively only an approximation since due to imperfect blending not all samples analyzed are identical to the composition of the overall package. Qualitatively, however, both 8-day samples were found to be free flowing with no signs of caking and to have a clean acetaldehyde taste. The 42-day sample stored at 85% RH. was somewhat caked but had a clean acetaldehyde taste; whereas, the 70% RH. sample showed only slight signs of caking and possessed a clean acetaldehyde taste.

Evaluation of additional anhydrous crystalline material has shown that organic crystals such as fiumaric acid and inorganic crystals such as sodium chloride are able to fix low levels (less than 1%) of clean acetaldehyde. Additionally, such volatile flavoring substances such as maltol, and natural and synthetic roasted coflee aromas (e.g. synthetic grinder gas and the like) have been successfully fixed within sucrose crystals.

It will be apparent that there are variations and modifications of this invention, and that the examples and typical operating conditions may be varied without departing from the scope of the invention.

Having thus described the invention, what is claimed 15:

1. A method for producing a solid flavoring composition containing low levels of volatile flavoring compounds comprising the steps of:

(a) forming a supersaturated aqueous solution of sucrose, said solution also containing a volatile flavoring compound,

(b) crystallizing sucrose from the solution to fix a portion of the volatile flavoring compound within individual sucrose crystals at a level of from about 0.1% to about 0.5% by weight of the crystal, and thereafter,

(c) drying the crystals.

2. The method of claim 1 wherein the crystals are separated from solution and then dried.

3. The method of claim 2 wherein the volatile flavoring compound is acetaldehyde.

4. The method of claim 1 wherein seed material is added to the supersaturated solution in order to initiate crystallization.

5. The method of claim 4 wherein the crystals are separated from the solution and then dried.

6. The method according to claim 5 wherein the crystallization takes place under vacuum conditions.

7. The method according to claim 6 wherein the volatile flavoring compound is acetaldehyde.

8. A solid moisture-stable flavoring composition comprising sucrose food crystals containing from about 0.1% to about 0.5% by weight of a volatile flavoring compound fixed within its crystal structure.

9. The flavoring composition of claim 8 wherein the volatile flavoring material is acetaldehyde.

10. The flavoring composition of claim 9 wherein the composition is incorporated into a powdered gelatin dessert mix.

11. The flavoring composition of claim 9 wherein the 2,786,766 3/1957 Meuel 99140 R flavoring composition 1 is incorporated into a; powdcrpd 3,314,8031- 441967 -Dame;et; aL- 9.9 1140 beyerage mix. y 1 1 Referens Cit ed I MORRIS WOLK, Primary Examiner I UNITED STATES PAIENIS Agfijz As stam Earning? 

